JPH0424433B2 - - Google Patents
Info
- Publication number
- JPH0424433B2 JPH0424433B2 JP20796387A JP20796387A JPH0424433B2 JP H0424433 B2 JPH0424433 B2 JP H0424433B2 JP 20796387 A JP20796387 A JP 20796387A JP 20796387 A JP20796387 A JP 20796387A JP H0424433 B2 JPH0424433 B2 JP H0424433B2
- Authority
- JP
- Japan
- Prior art keywords
- ions
- phosphate
- zinc
- iron
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000011282 treatment Methods 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- 229910052742 iron Inorganic materials 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 23
- -1 iron ions Chemical class 0.000 claims description 19
- 229910019142 PO4 Inorganic materials 0.000 claims description 18
- 239000010452 phosphate Substances 0.000 claims description 18
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 12
- 238000005482 strain hardening Methods 0.000 claims description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000005461 lubrication Methods 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229940085991 phosphate ion Drugs 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 11
- 239000000344 soap Substances 0.000 description 11
- IQBJFLXHQFMQRP-UHFFFAOYSA-K calcium;zinc;phosphate Chemical compound [Ca+2].[Zn+2].[O-]P([O-])([O-])=O IQBJFLXHQFMQRP-UHFFFAOYSA-K 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000005755 formation reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000005069 Extreme pressure additive Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000712 Boron steel Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AWUCVROLDVIAJX-UHFFFAOYSA-N alpha-glycerophosphate Natural products OCC(O)COP(O)(O)=O AWUCVROLDVIAJX-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 102220358403 c.89C>G Human genes 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- WQQALHZJAGFRSS-UHFFFAOYSA-J calcium zinc dihydrogen phosphate phosphate Chemical compound P(=O)([O-])([O-])[O-].P(=O)([O-])(O)O.[Ca+2].[Zn+2] WQQALHZJAGFRSS-UHFFFAOYSA-J 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229940005989 chlorate ion Drugs 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 238000010273 cold forging Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- AWUCVROLDVIAJX-GSVOUGTGSA-N sn-glycerol 3-phosphate Chemical compound OC[C@@H](O)COP(O)(O)=O AWUCVROLDVIAJX-GSVOUGTGSA-N 0.000 description 1
- 239000008149 soap solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- OSKILZSXDKESQH-UHFFFAOYSA-K zinc;iron(2+);phosphate Chemical compound [Fe+2].[Zn+2].[O-]P([O-])([O-])=O OSKILZSXDKESQH-UHFFFAOYSA-K 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/22—Orthophosphates containing alkaline earth metal cations
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Forging (AREA)
- Lubricants (AREA)
- Chemical Treatment Of Metals (AREA)
Description
〔産業上の利用分野〕
本発明は、伸線、冷間鍜造、転造、伸管、ヘツ
ダー加工などに適用される鉄又はその合金の冷間
加工潤滑処理方法に関するものである。
〔従来技術〕
鉄又はその合金を冷間加工する場合、被加工機
と工具との摩擦及び摩耗を低減する為に被加工機
に潤滑処理を施すのが通常であり、比較的低加工
度のものに対しては、極圧添加剤や油性向上剤を
添加した油が施され、高加工度のものに対して
は、リン酸亜鉛系処理液にてリン酸塩皮膜を生成
させ、その上にナトリウム石鹸又は金属石鹸等の
潤滑剤が施されていた。
更に、前記リン酸塩皮膜の潤滑性を改善して、
リン酸亜鉛カルシウム系皮膜を生成させる処理液
が開発され、特公昭60−20463号公報に開示され
ている。同処理液の組成は、カルシウムイオン
0.1〜0.35％、亜鉛イオン0.1〜1.5％、リン酸イオ
ン0.5〜3.0％、硝酸イオン3.0〜5.0％で、且つ亜
鉛イオンに対するカルシウムイオンの重量比が
0.1〜1.0及びリン酸イオンに対する硝酸イオンの
重量比が1.0〜5.0となつている。この処理液は70
〜85℃で適用され、生成した皮膜はリン酸亜鉛カ
ルシウムと、リン酸亜鉛と、リン酸亜鉛鉄などの
結晶の混合物であり、リン酸塩の皮膜重量が多
く、式で示したように、潤滑剤の石鹸との反応
性が良いため、金属石鹸の生成量が多く良好であ
る。
6C17H35COONa＋Me（PO4）2→３（C17H35CO）2Me＋2Na3P
O4……
〔発明が解決しようとする問題点〕
前記従来例においては、その処理温度70〜85℃
を必須要件としており、近年要求されている省エ
ネルギーに逆行するという問題点を有するばかり
でなく、生成された皮膜において、耐熱性の良い
リン酸亜鉛カルシウム（シヨルタイト）が10〜25
％と少ないため、一工程における断面減少率が80
％に達する強加工の場合には、加工中の被加工物
の表面温度が300℃を超えることもしばしばあり、
リン酸亜鉛カルシウムが少ないリン酸塩皮膜は、
熱分解や物理的破壊により、その潤滑性能が発揮
されないという問題点を有している。
〔問題点を解決するための手段〕
前記従来例の問題点を解決する具体的手段とし
て、鉄又はその合金を冷間加工する際、予め鉄イ
オン0.01〜2.0％、カルシウムイオン0.5〜3.5％、
亜鉛イオン0.3〜2.5％、リン酸イオン0.5〜5.0％、
硝酸イオン0.7〜12.0％の範囲の濃度で且つ亜鉛
イオンに対する鉄イオンの重量比がFe／Zn＝
0.005〜3.0、亜鉛イオンに対するカルシウムイオ
ンの重量比がCa／Zn＝0.5〜4.0のリン酸塩処理液
により35〜65℃で処理し、次いで潤滑剤処理を施
すことを特徴とする鉄又はその合金の冷間加工潤
滑処理方法を提供するものであり、特にリン酸塩
処理液中のカルシウム／亜鉛の比を高くすること
により、リン酸亜鉛カルシウムの含有率を増大さ
せると共に、鉄イオンを含有させて低温で処理
し、省エネルギーに寄与できるのである。
〔処理液組成の説明〕
本発明に係るリン酸塩皮膜化成処理液中の各イ
オンの濃度及び重量比において、鉄イオンは、大
部分が２価イオンとして存在しており、３価イオ
ンも一部混在している。0.01％未満であると皮膜
の化成性が低下して均一な皮膜が生成しないた
め、塑性加工時に焼付きが発生する。2.0％を超
えると皮膜化成性が低下し、又、処理液の配合比
率が変つてくるため液の管理が難しくなり作業性
が悪くなる。好ましいのは0.05〜0.5％である。
カルシウムイオンは0.5％未満であると、強加
工に必要なリン酸亜鉛カルシウム系皮膜の生成が
少なすぎてよくない。又、3.5％を超えても、増
加した分の効果が認められない。むしろ皮膜重量
が減少する傾向でよくない。好ましいのは1.0〜
2.0％である。
亜鉛イオンは0.3％未満であると皮膜重量が少
なくなりすぎたり、化成不良を起すため焼付きが
発生しやすくなる。2.5％を超えると、リン酸亜
鉛カルシウム系皮膜の生成が少なすぎてよくな
い。好ましい範囲は、0.5〜1.5％である。
リン酸イオンは、0.5未満であるとリン酸塩皮
膜の化成性が悪く、焼付きが発生する。５％を超
えても添加に見合う効果が得られない。好ましい
のは１〜３％である。硝酸イオンは、0.7％未満
では、被加工機の鉄又はその合金の腐食溶解性が
低下するため、化成反応が遅くなつてよくない。
12.0％を超えても、添加に見合う効果が得られな
い。好ましいのは1.5〜7.0％である。
カルシウムイオンと亜鉛イオンの重量比は、
Ca／Zn＝0.5未満であるとリン酸亜鉛カルシウム
系皮膜の生成量が少なく耐熱性が低下して強加工
に耐えられなくなり、4.0を超えると、その比に
見合う効果が得られない。むしろ皮膜重量が減少
してよくない。好ましいのは1.0〜2.0である。
鉄イオンと亜鉛イオンの重量比は、Fe／Zn＝
0.005未満である皮膜化成性が低下して不均一皮
膜となり強加工に耐えられなくなり、3.0を超え
ると皮膜化成性が低下して強加工に耐えられなく
なる。好ましいのは0.05〜1.0である。
処理液温度は35〜65℃の低温度である。これ
は、硝酸根の酸化力が弱く、２価の鉄イオンが３
価の鉄イオンにならないため、鉄イオンが処理液
中で安定している。70〜85℃の高温にすると、硝
酸根の酸化力が強く、鉄イオン触媒作用による酸
化力の強い亜硝酸に代り、それによつて２価の鉄
イオンが３価の鉄イオンになり、リン酸鉄として
沈澱して、処理液中の鉄イオンがなくなり、好ま
しくない。従つて、好ましい温度範囲は40〜55℃
である。このため、強力な酸化剤は２価の鉄イオ
ンが不安定となるため併用できないが、酸化力の
弱い例えば塩素酸イオンなどは用途に応じて併用
しても良い。
処理液の濃度は全酸度（TA）で管理する。鉄
鋼材料を腐食させるため、遊離のリン酸が処理液
中に存在し、これを遊離酸度（FA）で表わす。
リン酸塩皮膜の化成反応をスムーズに進めるた
め、TA，FA及びTA／FA（酸比）を管理する必
要がある。TA／FAは温度によつて良好な皮膜
化成ができる範囲が決つており、低温度の場合は
高く、高温度の場合は低い値となる。尚、酸比の
調整は水酸化ナトリウム、炭酸ナトリウム、水酸
化カリウム、アモンニア水等のアルカリやリン酸
などの酸で行うことができる。
前記した処理液に対して、ニツケル、コバル
ト、銅イオンの１種又は２種以上を添加すること
によつて、リン酸亜鉛カルシウム系皮膜の重量を
増加させることができ、潤滑性を向上する。これ
らのイオンの添加量は、0.01％未満では皮膜重量
を増加させる効果が少なく、又、0.4％を超えて
もそれ以上の効果が期待できない。従つて、好ま
しい範囲はニツケルイオンで0.05〜0.2％程度で
ある。尚、他の金属イオン、例えばマンガン、マ
グネシウム、チタン、ジルコニウムなどを潤滑性
に悪影響を及ぼさない範囲で含んでも良い。
更に前記処理液に対し、リン酸亜鉛カルシウム
の結晶を緻密にするため、例えば酒石酸、クエン
酸、グリセロリン酸などのキレート剤を0.01〜
0.05％程度の範囲で含ませても良い。
〔処理方法の説明〕
前記した処理液を用い、処理液温度を35〜65℃
の範囲にし、浸漬又はスプレー法にて10秒〜20分
間行う。皮膜化成反応を速めるためには予めコロ
イドチタン化合物を含有する表面調整用水溶液、
例えばプレパレンＺ（商標名、日本パーカライジ
ング(株)社製）などで被処理金属表面を処理した
り、リン酸塩処理液の濃度を高めることで可能と
なる。被処理金属をリン酸塩処理し、その表面に
リン酸塩皮膜を形成させた後、水洗又は水洗しな
いで乾燥もしくは乾燥することなく潤滑処理を行
う。
潤滑処理としては、アルカリ石鹸水溶液による
処理、金属石鹸含有液による処理、潤滑油処理、
固体潤滑処理等による方法が挙げられる。
アルカリ石鹸処理の例としては、ステアリン酸
ナトリウム等の脂肪酸石鹸の40〜100g／水溶
液に70〜90℃、１〜10分間浸漬処理し、乾燥して
潤滑皮膜を形成させるものがあり、金属石鹸処理
の例としては、ステアリン酸カルシウム、ステア
リン酸バリウム、ステアリン酸亜鉛等の脂肪酸の
金属塩の粉末又は溶媒分散液で処理させるものが
ある。潤滑油の例としては、油脂、合成油、鉱油
等を基油とし、極圧添加剤として硫黄化合物、リ
ン化合物、塩素化合物等を用いるものがある。金
属石鹸以外の固体潤滑剤の例として、２硫化モリ
ブデン、２硫化タングステン、フツ素樹脂、グラ
フアイト、ワツクス等の粉末又は溶媒分散液があ
る。又固体潤滑剤の基材表面に対する密着性を向
上させるために、樹脂を配合する場合もある。
処理される鉄又はその合金としては、例えば、
炭素鋼やSCM系、SNC系、SCr系、SM系、
SMC系、ボロン鋼などが挙げられ、リ酸塩処理
により、その表面にリン酸塩皮膜が生成するもの
である。
次に本発明についていくつかの実施例を挙げ、
比較例と対比して説明する。
実施例 １〜３
S30Cの電縫鋼管を酸洗、水洗し、表１のリン
酸塩処理液で夫々処理理し、次いで石鹸潤滑剤パ
ルーブー235（商品名、日本パーカライジング(株)社
製）、70g／、75℃５分間浸漬し、乾燥後、抽
伸機により表２の条件で引抜加工を行つた。その
結果は表３、表４に示す通りであつた。
[Industrial Field of Application] The present invention relates to a method for cold working lubrication of iron or its alloy, which is applied to wire drawing, cold forging, rolling, pipe drawing, header processing, and the like. [Prior art] When cold working iron or its alloys, the workpiece is usually lubricated to reduce friction and wear between the workpiece and the tool. For products, oil containing extreme pressure additives and oiliness improvers is applied, and for highly processed products, a phosphate film is generated using a zinc phosphate treatment solution, and then Lubricants such as sodium soap or metal soap were applied to the Furthermore, improving the lubricity of the phosphate film,
A treatment solution that produces a zinc-calcium phosphate film has been developed and disclosed in Japanese Patent Publication No. 60-20463. The composition of the treatment solution is calcium ions.
0.1-0.35%, zinc ion 0.1-1.5%, phosphate ion 0.5-3.0%, nitrate ion 3.0-5.0%, and the weight ratio of calcium ion to zinc ion is
0.1 to 1.0, and the weight ratio of nitrate ions to phosphate ions is 1.0 to 5.0. This treatment liquid is 70
Applied at ~85°C, the resulting film is a mixture of calcium zinc phosphate, zinc phosphate, and crystals such as zinc iron phosphate, with a high film weight of phosphate, as shown in Eq. Since the lubricant has good reactivity with soap, the amount of metal soap produced is large and good. 6C 17 H 35 COONa + Me (PO 4 ) 2 → 3 (C 17 H 35 CO) 2 Me + 2Na 3 P
O 4 ... [Problem to be solved by the invention] In the conventional example, the treatment temperature was 70 to 85°C.
is an essential requirement, which not only has the problem of going against the energy saving requirements that have been demanded in recent years, but also has the problem that the produced film contains 10 to 25
%, so the cross-sectional reduction rate in one process is 80%.
%, the surface temperature of the workpiece during machining often exceeds 300℃.
Phosphate films with low zinc calcium phosphate are
The problem is that the lubricating performance is not exhibited due to thermal decomposition or physical destruction. [Means for solving the problems] As a specific means for solving the problems of the conventional example, when cold working iron or its alloy, 0.01 to 2.0% of iron ions, 0.5 to 3.5% of calcium ions,
Zinc ion 0.3-2.5%, phosphate ion 0.5-5.0%,
The concentration of nitrate ions ranges from 0.7 to 12.0%, and the weight ratio of iron ions to zinc ions is Fe/Zn=
0.005 to 3.0, a weight ratio of calcium ions to zinc ions of Ca/Zn is treated at 35 to 65°C with a phosphate treatment solution of 0.5 to 4.0, and then treated with a lubricant. In particular, by increasing the calcium/zinc ratio in the phosphate treatment solution, the content of zinc calcium phosphate is increased, and iron ions are also contained. It can be processed at low temperatures, contributing to energy savings. [Explanation of treatment liquid composition] In terms of the concentration and weight ratio of each ion in the phosphate film chemical conversion treatment liquid according to the present invention, most iron ions exist as divalent ions, and trivalent ions also exist as monovalent ions. Parts are mixed. If it is less than 0.01%, the chemical conversion properties of the film will decrease and a uniform film will not be formed, resulting in seizure during plastic working. If it exceeds 2.0%, the film formation properties will decrease, and the mixing ratio of the treatment liquid will change, making it difficult to manage the liquid and impairing workability. Preferred is 0.05-0.5%. If the calcium ion content is less than 0.5%, the formation of the zinc calcium phosphate film required for heavy processing is too small, which is not good. Moreover, even if it exceeds 3.5%, the effect of the increase is not recognized. Rather, the film weight tends to decrease, which is not good. Preferably 1.0~
It is 2.0%. If the zinc ion content is less than 0.3%, the weight of the film will be too low, or chemical formation will be poor, making it more likely that seizure will occur. If it exceeds 2.5%, the formation of a zinc calcium phosphate film will be too small, which is not good. The preferred range is 0.5-1.5%. If the phosphate ion content is less than 0.5, the chemical formation properties of the phosphate film will be poor and seizure will occur. Even if it exceeds 5%, the effect commensurate with the addition cannot be obtained. A preferable range is 1 to 3%. If the nitrate ion content is less than 0.7%, the corrosion solubility of iron or its alloy in the machine to be machined will be reduced, and the chemical reaction will be slowed down, which is not good.
Even if it exceeds 12.0%, the effect commensurate with the addition cannot be obtained. The preferred range is 1.5-7.0%. The weight ratio of calcium ions and zinc ions is
When Ca/Zn=less than 0.5, the amount of zinc-calcium phosphate film produced is small and the heat resistance decreases, making it unable to withstand strong working, while when it exceeds 4.0, no effect commensurate with the ratio can be obtained. Rather, the weight of the film decreases, which is not good. The preferred value is 1.0 to 2.0. The weight ratio of iron ions and zinc ions is Fe/Zn=
When the value is less than 0.005, the film formation property decreases, resulting in a non-uniform film that cannot withstand strong processing, and when it exceeds 3.0, the film formation property decreases and becomes unable to withstand strong processing. The preferred value is 0.05 to 1.0. The processing liquid temperature is a low temperature of 35 to 65°C. This is because the oxidizing power of the nitrate radical is weak, and the divalent iron ion is 3
Iron ions are stable in the processing solution because they do not become valent iron ions. When the temperature is raised to a high temperature of 70 to 85℃, the oxidizing power of the nitrate group is strong, and it is replaced by the strong oxidizing power of nitrous acid due to the iron ion catalytic action, thereby divalent iron ions become trivalent iron ions, and phosphoric acid This is undesirable because it precipitates as iron and eliminates iron ions in the treatment solution. Therefore, the preferred temperature range is 40-55℃
It is. For this reason, a strong oxidizing agent cannot be used in combination because the divalent iron ion becomes unstable, but a weak oxidizing agent such as chlorate ion may be used in combination depending on the purpose. The concentration of the treatment solution is controlled by total acidity (TA). To corrode steel materials, free phosphoric acid is present in the treatment solution and is expressed as free acidity (FA).
In order to smoothly proceed with the chemical conversion reaction of the phosphate film, it is necessary to control TA, FA, and TA/FA (acid ratio). The range in which good film formation can be achieved for TA/FA is determined by temperature, and the value is high at low temperatures and low at high temperatures. Note that the acid ratio can be adjusted using an alkali such as sodium hydroxide, sodium carbonate, potassium hydroxide, or ammonia water, or an acid such as phosphoric acid. By adding one or more of nickel, cobalt, and copper ions to the above-mentioned treatment liquid, the weight of the zinc calcium phosphate coating can be increased and the lubricity can be improved. If the amount of these ions added is less than 0.01%, the effect of increasing the film weight is small, and if it exceeds 0.4%, no further effect can be expected. Therefore, the preferable range is about 0.05 to 0.2% of nickel ions. In addition, other metal ions such as manganese, magnesium, titanium, zirconium, etc. may be included within a range that does not adversely affect the lubricity. Furthermore, in order to make the crystals of zinc calcium phosphate dense, a chelating agent such as tartaric acid, citric acid, or glycerophosphoric acid is added to the treatment solution in an amount of 0.01 to 100%.
It may be included within a range of about 0.05%. [Explanation of treatment method] Using the treatment liquid described above, the treatment liquid temperature was set at 35 to 65°C.
Dip or spray for 10 seconds to 20 minutes. In order to accelerate the film formation reaction, a surface conditioning aqueous solution containing a colloidal titanium compound,
For example, this can be achieved by treating the surface of the metal to be treated with Prepalene Z (trade name, manufactured by Nippon Parkerizing Co., Ltd.) or by increasing the concentration of the phosphate treatment solution. After the metal to be treated is subjected to phosphate treatment and a phosphate film is formed on its surface, a lubrication treatment is performed by washing with water, drying without washing with water, or drying without drying. Lubrication treatments include treatment with an aqueous alkaline soap solution, treatment with a liquid containing metal soap, treatment with lubricating oil,
Examples include methods such as solid lubrication treatment. Examples of alkaline soap treatment include immersion treatment in 40 to 100 g/aqueous solution of fatty acid soap such as sodium stearate at 70 to 90°C for 1 to 10 minutes, and drying to form a lubricating film. Examples include those treated with powders or solvent dispersions of metal salts of fatty acids such as calcium stearate, barium stearate, and zinc stearate. Examples of lubricating oils include oils, synthetic oils, mineral oils, etc. as base oils and extreme pressure additives such as sulfur compounds, phosphorus compounds, chlorine compounds, etc. Examples of solid lubricants other than metal soap include powders or solvent dispersions of molybdenum disulfide, tungsten disulfide, fluorine resins, graphite, wax, and the like. Further, in order to improve the adhesion of the solid lubricant to the surface of the base material, a resin may be added. Examples of the iron or alloy thereof to be treated include:
Carbon steel, SCM series, SNC series, SCr series, SM series,
Examples include SMC type steel and boron steel, and a phosphate film is formed on the surface by phosphate treatment. Next, some examples of the present invention will be given,
This will be explained in comparison with a comparative example. Examples 1 to 3 S30C electric resistance welded steel pipes were pickled, washed with water, and treated with the phosphate treatment solutions shown in Table 1, respectively, and then treated with the soap lubricant Paruvoo 235 (trade name, manufactured by Nippon Parkerizing Co., Ltd.), 70g/, immersed at 75°C for 5 minutes, dried, and then drawn using a drawing machine under the conditions shown in Table 2. The results were as shown in Tables 3 and 4.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
前記表３、４から明らかなように、実施例１〜
３は充分な皮膜重量が得られ、その皮膜重量に対
するリン酸亜鉛カルシウム系皮膜成分が多く、且
つ金属石鹸量もバランス良く多くなつており、引
抜加工の結果、ダイス及びプラグにおけるパイプ
の焼付発生がなく、潤滑性は良好であつた。
実施例 ４〜７
Ｓ−45Cの線材（10φ×100mm）を酸洗、水洗
し、表５のリン酸塩処理液で夫々処理し、次いで
水洗してから石鹸潤滑剤パルーブ２３５（商品
名、日本パーカライジング(株)社製）、70g／、
75℃で５分間浸漬し、乾燥後バウデン式摩擦摩耗
試験機（EFM−４、東洋ボールドウイン社製）
で、表６の条件により焼付（摩擦係数0.2以上）
までの摺動回数を測定した。その結果は表７、表
８に示す通りであつた。[Table] As is clear from Tables 3 and 4 above, Examples 1-
3 has a sufficient coating weight, has a large zinc phosphate calcium phosphate coating component relative to the coating weight, and has a well-balanced amount of metal soap, and as a result of the drawing process, there is no seizure of the pipe in the die or plug. The lubricity was good. Examples 4 to 7 S-45C wire rods (10 φ x 100 mm) were pickled, washed with water, treated with the phosphate treatment solution shown in Table 5, and then washed with water before applying the soap lubricant Parube 235 (trade name, Japan). Parkerizing Co., Ltd.), 70g/,
Immerse at 75°C for 5 minutes, dry and then use a Bauden friction and wear tester (EFM-4, manufactured by Toyo Baldwin).
Seizure occurs under the conditions in Table 6 (friction coefficient 0.2 or more).
The number of sliding movements was measured. The results were as shown in Tables 7 and 8.
【表】【table】
【表】【table】
【表】【table】
以上説明したように、本発明に係る冷間加工潤
滑処理方法は、処理液の各成分濃度と、各成分の
亜鉛イオンとの重量比を特定し、更に処理温度を
低温に特定することにより、鉄又はその合金の冷
間加工における苛酷条件に充分耐え得るだけの潤
滑性を付与することができ、それによつて冷間加
工工具の使用寿命も著しく延長させることができ
るという優れた効果を奏する。
又、前記した通り低温領域で処理できるので、
省エネルギーに大きく寄与する等の優れた効果も
奏する。
As explained above, the cold working lubrication treatment method according to the present invention specifies the concentration of each component of the treatment liquid and the weight ratio of each component to zinc ions, and further specifies the treatment temperature to be low. It has the excellent effect of providing sufficient lubricity to withstand the severe conditions during cold working of iron or its alloys, thereby significantly extending the service life of cold working tools. In addition, as mentioned above, it can be processed in a low temperature range, so
It also has excellent effects such as greatly contributing to energy conservation.
Claims (1)
オン0.01〜2.0％、カルシウムイオン0.5〜3.5％、
亜鉛イオン0.3〜2.5％、リン酸イオン0.5〜5.0％、
硝酸イオン0.7〜12.0％の範囲の濃度で且つ亜鉛
イオンに対する鉄イオンの重量比がFe／Zn＝
0.005〜3.0、亜鉛イオンに対するカルシウムイオ
ンの重量比がCa／Zn＝0.5〜4.0のリン酸塩処理液
により35〜65℃で処理し、次いで潤滑剤処理を施
すことを特徴とする鉄又はその合金の冷間加工潤
滑処理方法。 ２ リン酸塩処理液に、ニツケル、銅、コバルト
の１種又は２種以上のイオンが全体量で0.01〜
0.4％含まれる前記１項記載の鉄又はその合金の
冷間加工潤滑処理方法。[Claims] 1. When cold working iron or its alloy, 0.01 to 2.0% iron ions, 0.5 to 3.5% calcium ions,
Zinc ion 0.3-2.5%, phosphate ion 0.5-5.0%,
The concentration of nitrate ions ranges from 0.7 to 12.0%, and the weight ratio of iron ions to zinc ions is Fe/Zn=
0.005 to 3.0, a weight ratio of calcium ions to zinc ions of Ca/Zn is treated at 35 to 65°C with a phosphate treatment solution of 0.5 to 4.0, and then treated with a lubricant. cold working lubrication treatment method. 2 The phosphate treatment solution contains one or more ions of nickel, copper, and cobalt in a total amount of 0.01~
The method for cold working lubrication of iron or its alloy according to item 1 above, containing 0.4%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20796387A JPS6452084A (en) | 1987-08-21 | 1987-08-21 | Lubricating method in cold-working iron or its alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20796387A JPS6452084A (en) | 1987-08-21 | 1987-08-21 | Lubricating method in cold-working iron or its alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6452084A JPS6452084A (en) | 1989-02-28 |
| JPH0424433B2 true JPH0424433B2 (en) | 1992-04-27 |
Family
ID=16548422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20796387A Granted JPS6452084A (en) | 1987-08-21 | 1987-08-21 | Lubricating method in cold-working iron or its alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6452084A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6454585B2 (en) * | 2015-03-31 | 2019-01-16 | 株式会社神戸製鋼所 | Continuous surface treatment method for steel wire |
-
1987
- 1987-08-21 JP JP20796387A patent/JPS6452084A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6452084A (en) | 1989-02-28 |
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